Reactions Between Liquid Metal Alloys and Doped (Semiconducting) Aluminosilicate Glassmelts

库珀-0071325计划研究的基础是PI小组的发现，这些发现导致了浮法玻璃工艺的预测性动态反应模型。在“传统”浮法玻璃中(将钠钙硅酸盐熔体漂浮在纯锡熔体上制成的平板玻璃，最高温度为~1100oC)，反应的巨大驱动力(能量)最快地被由电子空穴和网络修饰阳离子的扩散运动主导的氧化还原动力学所耗散。Pi的模型解释了浮法玻璃中化学分布的许多特殊特征。结合浮法合金设计的溶液热力学，该模型被用于将浮法玻璃工艺外推到1400oC以上的温度，从而为浮法加工具有明显耐火成分的平板玻璃(例如，用作高端平板显示器的基板)打开了可能性。该模型还提出了一种理解框架，在该框架中，玻璃成分和浮法介质成分可以一起设计，以创造具有独特物理化学性质和性能的高附加值平板玻璃。这项研究是设计具有独特性能的平板玻璃的第一步。PI计划对熔融的铝硅酸盐溶液与熔融金属溶液之间的反应(S)进行实验和理论研究，具体地说：(1)硅酸盐-金属界面上的氧化还原电偶所涉及的驱动力和化学物种，(2)反应中铝硅酸盐玻璃熔体中化学扩散的物理机制(S)，以响应伴随整个反应的化学扩散。此外，通过与液态金属合金的反应，反应玻璃熔体的物理性质/特征允许产生可能具有独特催化的表面，具体地说，将有两个实验推力：(A)时间/温度/距离(即进入玻璃熔体)分析铜-37Ge(at.%)与无铁和铁掺杂的硼铝硅酸钠(NaBS，其类似于Pyrex)与镁铝硅酸盐玻璃熔体之间的反应，以及(B)作为受化学扩散影响的成分的函数的反应玻璃熔体的结构和化学(径向分布函数和电子损失光谱)分析，在预期的横向分辨率为5-10 nm，使用能量过滤的电子显微镜。这个项目由材料研究部(数学和物理科学局)的陶瓷计划和化学和运输系统司(工程局)的过程和反应工程计划共同资助。

Abstract - Cooper - 0071325The foundation for the research planned are discoveries in the PI's group that resulted in a predictive dynamic reaction model for the float-glass process. In "traditional" float glass (flat glass prepared from floating a soda-lime silicate melt on pure molten tin, highest temperature of ~1100oC), the large driving-force (energy) of reaction is dissipated most rapidly by a redox dynamic that is dominated by the diffusive motions of electron holes and network-modifying cations. The PI's model explains many idiosyncratic features of the chemical profile in float glass. Combined with solution thermodynamics for float-alloy design, the model was used to extrapolate the float-glass process to temperatures in excess of 1400oC, opening the possibility of float-processing flat glass of distinctly refractory compositions (e.g., for application as substrates in high-end flat-panel displays). The model also suggests a framework of understanding in which glass composition and float-medium composition can be engineered together so as to create high-value-added flat glass with unique physiochemical properties and performance. The research planned represents the first steps to "designer"-flat-glass of unique properties.The PI plans to conduct an experimental and theoretical study of the reaction(s) between molten aluminosilicate solutions with molten metal solutions, specifically:(1) the driving force and chemical species involved in the redox couple at the silicate-metal interface,(2) the physical mechanism(s) of chemical diffusion in the reacting aluminosilicate glassmelt in response to the chemical diffusion accompanying the overall reaction.In addition, the physical properties/characteristics of the reacted glassmelt via its reaction with the liquid metal alloy allows for creation of a surface with perhaps unique catalytic, photonic or thermochemical (e.g., crystalline nucleation) responses.Specifically, there will be two experimental thrusts: (a) time/temperature/distance (i.e., into the glassmelt) analyses of reactions between Cu-37Ge (at.%) and both iron-free and ferric-iron-doped sodium aluminoborosilicate (NABS which is similar to Pyrex) and magnesium aluminosilicate glassmelts, and (b) structural and chemical (radial distribution function and electron loss spectroscopy) analyses of reacted glassmelts as functions of chemical-diffusion-affected composition, at an anticipated lateral resolution of 5-10 nm, using energy-filtered transmission electron microscopy.This project is being co-funded by the Ceramics Program in the Division of Materials Research (Mathematical and Physical Sciences Directorate) and the Process and Reaction Engineering Program in the Division of Chemical and Transport Systems (Engineering Directorate).